CN101901845A - Metal oxide electrode and manufacture method thereof and dye-sensitized solar cell - Google Patents
Metal oxide electrode and manufacture method thereof and dye-sensitized solar cell Download PDFInfo
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- CN101901845A CN101901845A CN2010101934617A CN201010193461A CN101901845A CN 101901845 A CN101901845 A CN 101901845A CN 2010101934617 A CN2010101934617 A CN 2010101934617A CN 201010193461 A CN201010193461 A CN 201010193461A CN 101901845 A CN101901845 A CN 101901845A
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- metal oxide
- electrode
- dye
- solar cell
- oxide layer
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- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/204—Light-sensitive devices comprising an oxide semiconductor electrode comprising zinc oxides, e.g. ZnO
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides metal oxide electrode and manufacture method thereof and dye-sensitized solar cell.The invention provides excellent aspect the mechanical strength of metal oxide layer and can excessively not damage battery behavior and the dye-sensitized solar cell that improves durability with metal oxide electrode, at the dye-sensitized solar cell of excellence aspect battery behavior and the durability etc.Dye-sensitized solar cell of the present invention has matrix and the metal oxide layer that is arranged on this matrix with metal oxide electrode, and described metal oxide layer contains metal oxide and phosphoric acid based surfactant.Preferably, contain the described phosphoric acid based surfactant of 0.1～30 weight % with respect to described metal oxide.
Description
Technical field
The present invention relates to the manufacture method of dye-sensitized solar cell with metal oxide electrode and dye-sensitized solar cell and metal oxide electrode.
Background technology
Made a report by Gratzel etc., the main points of this report are: by using the porous titanium oxide electrode, thereby obtained to have the dye-sensitized solar cell (with reference to J.Am.Chem.Soc.115 (1993) 6382) of the performance that can be equal to mutually with non-crystal silicon solar cell.In addition, in the recent period, no matter be both at home and abroad, in various research aircrafts are enough, all extensively carrying out the research for application and development of pigment sensitized solar cell.For example, except above-mentioned titanium oxide, reported: the various metal oxides of the metal oxide of niobium oxide, zinc oxide, tin oxide and indium oxide etc. and their mixed system etc. also can be brought into play photoelectric converting function.
As the manufacture method of above-mentioned metal oxide electrode, the general use coated the surface of conductive board and the method for film forming in addition with the coating fluid of the colloidal solution of the microparticle of metal oxide or slurries etc.
In order to make metal oxide electrode give full play to its function, metal oxide particle each other strong bonded and the strong bonded on metal oxide microparticle and conductive board surface will become extremely important.In order to reach these purposes, following method is arranged in the known prior art: the coating fluid of the organic binder bond composition of an amount of polyethylene glycol etc. has been added in modulation, and this coating fluid is applied on the substrate, afterwards, burn till with the high temperature more than 400 ℃, thereby carry out film forming.Yet, use and so must carry out the method that high temperature burns till processing the damage of substrate can take place, thus in fact can not use the substrate that contains resin material, thereby the problem that is restricted of its result purposes of existing the electrode that is obtained.In addition, because the energy that is applied is bigger, so also have the big problem of carrying capacity of environment.
In view of such problem, in patent documentation 1, instead the high temperature processing method of burning till has proposed following various processing methods: (i) the following ultraviolet light of irradiation 400nm, (ii) to heat less than 350 ℃ more than or equal to 50 ℃, (iii) irradiating microwaves etc.In addition, proposed a kind of method in patent documentation 2: the dispersion liquid that will contain metal-oxide semiconductor (MOS) microparticle and resin glue is applied on the transparency conducting layer, carry out the easy fired about 150 ℃, afterwards, described resin glue is carried out degreasing, thereby form the metal-oxide semiconductor (MOS) porous layer.Yet, in these methods, become branch to residue in the metal oxide layer as the organic binder bond of must composition and being matched with in the coating fluid, so exist the problem that is difficult to realize good battery behavior.
On the other hand, in patent documentation 3 to 5, proposed also can realize the manufacture method of the metal oxide layer of high battery behavior with the K cryogenic treatment of 150 ℃ of following degree.Specifically be to adopt not the organic binder bond components matching in the colloidal solution of metal oxide microparticle or the constituted mode in the slurry.Yet, in these methods, metal oxide particle each other and the associativity between metal oxide microparticle and the conductive board surface abundant not enough, so in test such as the durability (long-term reliability) of high temperature and humidity test and temperature cycling test etc., exist the problem that metal oxide layer generation breakage or metal oxide layer are peeled off from the conductive board surface etc.
The prior art document:
Patent documentation:
Patent documentation 1: TOHKEMY 2001-357896 communique
Patent documentation 2: TOHKEMY 2007-103310 communique
Patent documentation 3: TOHKEMY 2004-119129 communique
Patent documentation 4: TOHKEMY 2005-222838 communique
Patent documentation 5: TOHKEMY 2005-251591 communique
Summary of the invention
The present invention In view of the foregoing makes, its purpose is, provides a kind of mechanical strength (film-strength, dhering strength) of metal oxide layer excellent and can excessively not damage battery behavior and can make dye-sensitized solar cell that durability (long-term reliability) improves with the excellent dye-sensitized solar cell of metal oxide electrode, battery behavior and durability (long-term reliability) and can reproducibility simple and easy well and stablize the manufacture method of manufacturing metal oxide electrode as described above with low cost.
The inventor found that: use phosphoric acid based surfactant by replacing above-mentioned existing organic binder bond composition, can address the above problem, to such an extent as to finished the present invention through concentrated research repeatedly.
That is, dye-sensitized solar cell of the present invention has matrix and the metal oxide layer that is arranged on this matrix with metal oxide electrode, and described metal oxide layer contains metal oxide and phosphoric acid based surfactant.
The inventor is measuring above-mentioned dye-sensitized solar cell with after the characteristic of metal oxide electrode, distinguished that its metal oxide layer compares with the metal oxide layer of prior art, mechanical strength (film-strength and dhering strength) has had tremendous raising; And distinguished that also its durability of dye-sensitized solar cell (long-term reliability) of using this metal oxide layer and making has had significant raising; Further distinguished on this basis: the reduction that just is connected in the battery behavior that brings inevitably under the situation that is combined with machine binding agent composition is also obviously suppressed.The detailed mechanism of action that obtains such effect is also by clearly, but for example does following inferring.
As previously discussed, in order to improve the mechanical strength of metal oxide layer, preferably with the organic binder bond components matching in metal oxide layer.Yet, if as prior art with the organic binder bond components matching in metal oxide layer, will hinder support (absorption) of sensitizing coloring matter so to the surface of metal oxide, the wettability reduction etc. of metal oxide layer perhaps takes place and might hinder the immersion of electrolyte, so the tendency of obvious damage battery behavior is arranged.
On the one hand, under situation about phosphoric acid based surfactant being matched with in the metal oxide layer, can suppress the obvious reduction of such as previously discussed battery behavior.Its reason is also uncertain, but also be considered to: the phosphate of a plurality of electrophilics metallic atom preferential and metal oxide surface interacts, the result forms new energy level at metal oxide surface, thus have can responding to visible light band gap (band gap).
On the other hand, even phosphoric acid based surfactant also is the characteristic with low bubble in surfactant, therefore, even this phosphoric acid based surfactant is made an addition in the slurry or colloidal solution of metal oxide particle, can not observe bubble yet and take place.In general, the bubble that is blended in slurry or the colloidal solution also can enter into film (metal oxide layer, metal oxide film), if, cause that so probably the mechanical strength of formed metal oxide layer descends so bubble as described above is present in slurry or the colloidal solution.Under such meaning, think that also the use of phosphoric acid based surfactant is very favourable on the mechanical strength this point that improves film.In addition, the formation element of phosphate and transparency electrode (for example metallic element of In and Sn etc.) also can form firm associative key, so it is considered to significantly high with the dhering strength of base material.
But effect is not limited to this.
Described metal oxide layer preferably has the loose structure that the metal oxide particle cohesion forms.Because the cooperation of phosphoric acid based surfactant, metal oxide particle combines each other and between metal oxide particle and the conductive board surface securely, thereby the mechanical strength of metal oxide layer is significantly improved, and durability is significantly improved.
Described phosphoric acid based surfactant is preferably 0.1～30 weight % with respect to the content of described metal oxide.By the content of phosphoric acid based surfactant is adjusted to this scope, thus just can realize prior art the having both of the battery behavior that can not accomplish and durability (long-term reliability).
Dye-sensitized solar cell of the present invention can effectively utilize the dye-sensitized solar cell metal oxide electrode of the invention described above, and it comprises: have matrix and the metal oxide electrode that is arranged at the metal oxide layer on this matrix; With described metal oxide electrode be relative to the configuration to electrode; And be arranged at described metal oxide electrode and described to the electrolyte between the electrode; Described metal oxide layer contains metal oxide and phosphoric acid based surfactant, and has supported sensitizing coloring matter.Because reason same as described above, described metal oxide layer preferably have the loose structure that the metal oxide particle cohesion forms, described phosphoric acid based surfactant is preferably 0.1～30 weight % with respect to the content of described metal oxide.
The manufacture method of metal oxide electrode of the present invention can be made the dye-sensitized solar cell metal oxide electrode of the invention described above effectively, this metal oxide electrode has matrix and the metal oxide layer that is arranged on this matrix, and described manufacture method comprises: preparation contains the operation of the concoction of metal oxide particle and phosphoric acid based surfactant; Described concoction is placed operation on the matrix.According to this manufacture method, can reproducibility simple and easy well and stably make such as previously described metal oxide electrode at low cost.
According to the present invention, can be implemented in the mechanical strength aspect of metal oxide layer excellent and can excessively not damage battery behavior and the dye-sensitized solar cell that can improve durability with metal oxide electrode and aspect battery behavior and durability the dye-sensitized solar cell of excellence.And, do not need high temperature firing process as prior art, and can reproducibility simple and easy well and stably make at low cost, so improved productivity ratio and economy.
Description of drawings
Fig. 1 is the sectional view that the summary of expression dye-sensitized solar cell 100 and metal oxide electrode 14 constitutes.
Symbol description
11 support the electrode of pigment
12 matrixes
The 12a conductive surface
13 metal oxide layers
14 metal oxide electrodes
21 pairs of electrodes
The 22a conductive surface
22 matrixes
31 electrolyte
41 spacers
100 photo-electric conversion elements
Embodiment
Below be illustrated with regard to embodiments of the present invention.Also have, mark same-sign on identical key element, the repetitive description thereof will be omitted.In addition, about the position relation that waits up and down,, then be the position relation represented according to drawing as not special statement.Have, the dimension scale of drawing is not limited to illustrated ratio again.In addition, following execution mode is to be used to illustrate illustration of the present invention, and the present invention has more than and is defined in this execution mode.
Fig. 1 is the sectional view that the summary of the dye-sensitized solar cell of expression present embodiment constitutes.
Dye-sensitized solar cell 100 comprises: as the electrode that supports pigment 11 of work electrode, to electrode 21 and be arranged at this electrode that supports pigment 11 and to the electrolyte between the electrode 21 31.The electrode 11 that supports pigment with electrode 21 is clipped spacer 41 and is disposed by relative, in the electrode 11 that is supported pigment by this, enclosure space that electrode 21, spacer 41 and not shown seal member are divided into, enclosing has electrolyte 31.
The electrode 11 that supports pigment possesses metal oxide electrode 14, this metal oxide electrode 14 has porous metal oxide layer 13 on the conductive surface 12a of matrix 12, metal oxide layer 13 contains metal oxide and phosphoric acid based surfactant, and sensitizing coloring matter is supported (absorption) on this metal oxide layer 13.In other words, the formation of the electrode that supports pigment 11 of present embodiment is: on the conductive surface 12a of matrix 12, be laminated with the metal oxide layer 13 of sensitizing coloring matter that supported (absorption), the complex structure body of sensitizing coloring matter that promptly supported (absorption) on the surface of metal oxide.
As matrix 12, so long as matrix that at least can supporting metal oxide layer 13, its kind or size shape just have no particular limits so, for example, preferably use the matrix of tabular or sheet.As its object lesson, for example can enumerate: glass substrate; The plastic base of PETG, polyethylene, polypropylene, polystyrene etc.; Metal substrate or alloy substrate; Ceramic substrate; Perhaps duplexer of these substrates etc.In addition, matrix 12 preferably has light transmission, and being more preferably is the matrix of excellence aspect the light transmission in the visible region.Have, matrix 12 preferably has flexibility again.The structure of the various form that can bring into play its flexibility can be provided in the case.
Conductive surface 12a can be for example as conductivity PET film, by nesa coating being formed at matrix 12 first-class placing on the matrix 12.In addition, by the matrix 12 that use has conductivity, can omit conductive surface 12a is placed processing on the matrix 12.As the object lesson of nesa coating, for example can list indium-tin-oxide (ITO), indium-zinc oxide (IZO), SnO
2And InO
3, also have in addition fluorine mixed (dope) to SnO
2In the FTO that forms etc., but be not particularly limited in these.These materials both can have been distinguished use separately, also can make up multiple the use.The formation method of nesa coating is not special to be limited, and for example can use the known method of vapour deposition method, CVD method, spraying process, method of spin coating or infusion process etc.In addition, the thickness of nesa coating can be done suitable setting.Also have, the conductive surface 12a of matrix 12 can implement suitable surface modification treatment as required.Particularly, for example can enumerate: known surface treatments such as the preelectrolysis that utilize ungrease treatment, mechanical lapping processing, the impregnation process in the aqueous solution that surfactant, organic solvent or alkaline aqueous solution etc. carry out, utilizes electrolyte to carry out is handled, washing processings, dried still are not limited to these.
Metal oxide layer 13 is with TiO
2, ZnO, SnO
2, WO
3, Nb
2O
5Deng metal oxide as the porous semiconductor layer of main component.Metal oxide layer 13 also can contain metal, the oxide of these metals and the chalcogen compound of these metals of titanium, tin, zinc, iron, tungsten, zirconium, strontium, indium, cerium, vanadium, niobium, tantalum, cadmium, lead, antimony and bismuth etc.Also have, there is no particular limitation for the thickness of metal oxide layer 13, but preferred 0.05～50 μ m.
The phosphoric acid based surfactant that is contained in the metal oxide layer 13 is the surfactant with phosphate.Contain phosphoric acid based surfactant by making in the metal oxide layer 13, thereby can improve mechanical strength (film-strength, dhering strength) and durability (long-term reliability) tremendously, in addition, compare with the method for the prior art of adding organic binder bond, can also suppress the reduction of initial stage characteristic.From this point of view, to be contained in the metal oxide layer 13 be very important to phosphoric acid based surfactant.Preferred phosphoric acid based surfactant is the anionic surfactant with phosphate.More preferably, what have phosphoric acid on main polymer chain has the material of alkyl as side chain, specifically, for example can enumerate polyoxyethylene alkyl ether phosphoric acid and polyoxyethylene alkyl phenyl ether phosphoric acid etc.As the carbon number of this alkyl, be preferably about 12～20, the length that is contained in intramolecular alkyl not only can be single but also can be inequality.As its representation example, for example can enumerate polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene dodecylphenyl ether phosphoric acid, polyoxyethylene octadecyl ether phosphoric acid and polyoxyethylene octadecyl phenyl ether phosphoric acid etc., but be not limited to these compounds.
There is no particular limitation to be contained in the content of the phosphoric acid based surfactant in the metal oxide layer 13, but be preferably 0.1～30 weight %, more preferably 0.3～20 weight %, more preferably 0.5～15 weight %.The many more tendencies that have excellence aspect mechanical strength and durability more of the content of phosphoric acid based surfactant, on the other hand, the few more tendency of characteristic aspect excellence in the early stage that has more of the content of phosphoric acid based surfactant.Therefore, after having considered this balance, can appropriately set the content of phosphoric acid based surfactant.
There is no particular limitation for the formation method of metal oxide layer 13, can be suitable for known method.For example, carry out the method for sintering after can being set forth on the conductive surface 12a that the concoction that will contain metal oxide particle and phosphoric acid based surfactant places matrix 12 or on the conductive surface 12a that above-mentioned concoction is placed matrix 12 after carry out about 50～150 ℃, be preferably the method for the K cryogenic treatment about 70～150 ℃.According to these methods, can easily obtain to have the metal oxide layer 13 of the loose structure that the particle aggregation by metal oxide forms.Wherein, thereby apply the viewpoint that energy can reduce carrying capacity of environment, preferably carry out the method for the latter's about 50～150 ℃ K cryogenic treatment from when can using the substrate that contains resin, reducing.Also have, not special qualification of method with concoction places matrix surface can be suitable for existing known coating process etc.
The concoction that contains above-mentioned metal oxide particle and phosphoric acid based surfactant is preferably the blending liquid (for example dispersion liquid, colloidal solution or slurries etc.) that contains decentralized medium.Object lesson as decentralized medium, not special the qualification for example can be enumerated the various organic solvents of water, methyl alcohol, ethanol, isopropyl alcohol, butanols, carrene, acetone, acetonitrile, ethyl acetate, toluene, dimethyl formamide, ethoxy ethanol and cyclohexanone etc.Also have, these organic solvents both can have been distinguished use separately, also can make up multiple the use.The auxiliary agent that also can contain in addition, other surfactant, acid and intercalating agent etc. as required.
Being supported not special qualification of sensitizing coloring matter on metal oxide layer 13, can be the pigment arbitrarily in water colo(u)r, water-insoluble pigment and the oil-soluble pigment.According to as the needed performance of photo-electric conversion element, can suitably select to have the material of desired optical absorption band absorption spectrum.Object lesson as sensitizing coloring matter, for example can enumerate xanthene (xanthene) the class pigment of eosin W or W S etc., cumarin class pigment, the triphenylmethane pigment, cyanine class pigment, part cyanines class pigment, the phthalocyanines pigment, naphthalene phthalocyanines pigment, porphyrin class pigment, polypyridine metal complex dye etc., in addition also has bipyridyl ruthenium class pigment, azopigment, the quinones pigment, the quinone imides pigment, quinoline a word used for translation ketone pigment, side's acid (squarylium) class pigment, perylene (perylene) class pigment, indigo class pigment, Oxonol class pigment, polymethine class pigment, riboflavin class pigment etc., but be not particularly limited in these sensitizing coloring matters.Also have, these sensitizing coloring matters both can have been distinguished use separately, also can make up multiple the use.In addition, from the viewpoint that the pigment loading is increased, sensitizing coloring matter preferably has with metal oxide makes interactional adsorptivity group.As the object lesson of adsorptivity group, for example can enumerate carboxyl, sulfonic group or phosphate etc., but be not limited to these groups.
As the method that sensitizing coloring matter is supported on metal oxide layer 13, for example can enumerate the solution coat that metal oxide layer 13 be impregnated in the method in the solution that contains sensitizing coloring matter and will contain sensitizing coloring matter method to the metal oxide layer 13 etc.Can be at the solvent of this employed solution that contains sensitizing coloring matter according to the dissolubility of employed sensitizing coloring matter or intermiscibility etc., and suitably selected from the well known solvents of for example water, ethanol kind solvent, itrile group kind solvent and ketones solvent etc.
Also have, the electrode 11 (metal oxide electrode 14) that supports pigment also can have the intermediate layer between the conductive surface 12a of matrix 12 and metal oxide layer 13.The material in intermediate layer is not special to be limited, but preference is as metal oxide illustrated in above-mentioned nesa coating 12a etc.For example, can on the conductive surface 12a that metal oxide is separated out or is accumulated to matrix 12, form the intermediate layer by the known method of vapour deposition method, CVD method, spraying process, method of spin coating, infusion process or electrolysis method etc.Also have, the intermediate layer preferably has light transmission, further preferably has conductivity.In addition, there is no particular limitation for the thickness in intermediate layer, but about preferred 0.1～5 μ m.
Electrode 21 is made of the matrix 22 with conductive surface 22a, and this conductive surface 22a is to be disposed by relative with mode that the metal oxide layer 13 of the electrode 11 that supports pigment is faced.Matrix 22 and conductive surface 22a and above-mentioned matrix 12 and conductive surface 12a are same, can suitably adopt material known, for example, can use the material that also has nesa coating 12a except the matrix 12 with conductivity on matrix 12; Can also use film further to be formed at material that forms on the nesa coating 12a of matrix 12 etc. with metal, carbon and the electric conductive polymer etc. of platinum, gold, silver, copper, aluminium, indium, molybdenum, titanium etc.
As electrolyte 31, can suitably use redox electrolytes matter solution, this electrolyte solution is carried out semi-solid electrolyte that gelation forms or p N-type semiconductor N solid pores transferring material (solid-state hole transport material) be carried out material that film forming forms etc., general employed electrolyte in battery and solar cell etc.As the representational electrolyte solution of dye-sensitized solar cell, for example can enumerate the mixed solution of the acetonitrile solution, ethylene carbonate (ethylene carbonate) solution or propene carbonate (propylene carbonate) solution and these solution that contain iodine and iodide or bromine and bromide etc.Electrolytical concentration and various additives etc. can performance as requested be done suitably to set and select.As the object lesson of additive, for example can enumerate the inferior ethene of polyaniline, polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenyl (Polyphenylene vinylene, PPV) and the p type electric conductive polymer of the derivative of these materials etc.; By imidazoles (imidazolium) ion, pyridine (pyridinium) ion, triazole (triazolium) ion and the derivative of these materials and the molten salt that combination constituted of halide ion; Gelating agent; The oleogel agent; Dispersant; Surfactant; Stabilization agent etc., but be not particularly limited in these materials.
Embodiment
Below enumerate embodiment and comparative example describes the present invention in detail, but the present invention is not limited to these embodiment.
(embodiment 1)
At first, according to following program modulation titanium oxide colloid solution.
Add among the 0.1M aqueous solution of nitric acid 750ml while the isopropyl titanate (titanium isopropoxide) that stirs 125ml, spend these solution of further vigorous stirring 8 hours at 80 ℃.In the pressure vessel of teflon (registered trade mark) system, handle with 230 ℃ of autoclaves that the liquid that is obtained was carried out 16 hours.Then, stir the colloidal solution obtained and sediment is suspended again.Afterwards, remove the precipitation that does not suspend again, concentrate colloidal solution till titanium oxide concentration becomes 11 weight % with evaporator by suction strainer.Adding with respect to titania weight in resulting colloidal solution is the polyoxyethylene lauryl ether phosphoric acid (trade name: Phosphanol ML-220, eastern nation chemical industry system) of 5 weight %, afterwards, stirs 1 hour.
The colloidal solution that obtains as mentioned above with methyl alcohol dilution makes the titanium oxide colloid solution of embodiment 1 thus so that titanium oxide concentration becomes 2 weight %.
Then, use the titanium oxide colloid solution of the foregoing description 1 also to make metal oxide electrode (titanium oxide electrode) by following operation.
At first, on the surface of polycarbonate film base material, will be approximately the ITO spatter film forming of 600nm, thereby produce conductive polycarbonate film resin substrate (size: long 2.0cm, wide 1.5cm, thick 0.1mm with flexibility as the thickness of conducting film; Film resistor (sheetresistance): 30 Ω/).Then, with the thickness that is provided with the square hole of the wide 0.5cm of long 0.5cm is that the masking belt (masking tape) of 70 μ m is affixed on the conducting film of the above-mentioned conductive polycarbonate film resin substrate that obtains, towards this square hole spraying titanium oxide colloid solution, thereby give on the conducting film that is exposed in this square hole inboard titanium oxide colloid solution is attached.Afterwards, peel off masking belt, and with electric furnace 100 ℃ of following heat treated 30 minutes, thereby form the metal oxide layer (oxidation titanium film) that contains metal oxide and phosphoric acid based surfactant.Also have, the programming rate during heating is 2 ℃/min.
Then, in order to remove the nitric acid composition that is contained in the metal oxide layer that is obtained, and handle metal oxide layer with alkaline solution.Specifically be, the ammonia hydroxide/methanol dilute solution that uses 2 weight % is as alkaline solution, and metal oxide layer be impregnated in this solution 30 minutes, afterwards, take out metal oxide layer and cleaned with methyl alcohol, further 80 ℃ dry 10 minutes down.
By above operation, thereby acquisition has the metal oxide electrode (titanium oxide electrode) of the embodiment 1 of the metal oxide layer (oxidation titanium film) that contains metal oxide and phosphoric acid based surfactant on the conductive surface of matrix.Measure the thickness of this metal oxide layer, be about 6 μ m.
Also have, make metal oxide electrode same as described above (titanium oxide electrode), metal oxide layer (oxidation titanium film) is implemented thermogravimetric analysis (TGA) afterwards, confirm that polyoxyethylene lauryl ether phosphoric acid is 4.1 weight % with respect to the content of titanium oxide.The condition determination of this thermogravimetric analysis as described below.Use the TG/DTA22 device of NSK Electronics Co., Ltd system, 2mg and being positioned on the specimen mounting materialses, be placed in reference on the frame with reference to sample simultaneously, with the flow is that 300ml/ divides the He air to open beginning that makes as the atmosphere gas around the sample to circulate in the device, afterwards, be under 10 ℃/minute the heating schedule, to begin to heat up at programming rate, and measure the mass change (room temperature～500 ℃) of sample this moment from room temperature.
In addition, make metal oxide electrode same as described above (titanium oxide electrode), estimate the dhering strength of its metal oxide layer (oxidation titanium film) at conductive polycarbonate film resin substrate.The evaluation of dhering strength is that the gridiron pattern adhesive tape disbonded test (cross-cut cellophane tape peel test) according to JIS K5400 is carried out.Specifically be, at interval tessellated grid put into metal oxide layer (oxidation titanium film), use adhesive tape (CT24, Japanese NICHIBAN CO., LTD. system), make its driving fit after film surface, peel off adhesive tape with the belly of pointing with 1mm.Measurement is in the grid ratio (%) that remains in the metal oxide layer (oxidation titanium film) on the substrate behind the belt stripping test, and the grid ratio of the oxidation titanium film that consequently left behind after disbonded test is 96%, thereby confirms to have sufficient mechanical.
Afterwards, use the metal oxide electrode of the foregoing description 1, and make the electrode that supports pigment with following step.
Metal oxide electrode be impregnated in 3 * 10
-4The concentration of M has been added among the ethanol solution 20ml as (4,4 '-dicarboxylic acids-2,2 '-bipyridine) ruthenium (II) vulcabond of sensitizing coloring matter, and places 12 hours.After the placement, take out electrode and cleaned air dry with anhydrous acetonitrile.The electrode that affirmation is obtained is owing to support (absorption) of ruthenium pigment makes metal oxide layer become peony.
By above operation, thereby obtain to be supported the electrode that supports pigment of the embodiment 1 of the metal oxide layer that on the surface of metal oxide, forms having sensitizing coloring matter on the conductive surface of matrix.
Then, use the electrode that supports pigment of the foregoing description 1, and make dye-sensitized solar cell with following steps.
At first, so that the corresponding to mode of part of square hole part and the metal oxide layer that supports sensitizing coloring matter (oxidation titanium film), to be provided with the spacer of the long 1.5cm of long 0.5cm, wide 0.5cm square hole, wide 1.5cm, thick 70 μ m, put in metal oxide electrode (titanium oxide electrode) and go up and make it driving fit.So, the electrolyte filling in square hole part, will be put on spacer electrode 30 then, further use epoxy sealing around it, thereby produce the dye-sensitized solar cell of embodiment 1.At this, used as electrolyte to contain tetrapropyl ammonium iodide (tetrapropyl ammonium iodide) (0.4M) and the methoxypropionitrile solution of iodine (0.04M).In addition, as to electrode, used with the thickness evaporation of 100nm the conductive glass of platinum.
Use AM-1.5 (1000W/m
2) sun simulation device measure the battery behavior of the dye-sensitized solar cell of the embodiment 1 that is obtained.About battery behavior, measure open circuit voltage (Voc), density of photocurrent (Jsc), form factor (FF) and these 4 projects of conversion efficiency (η).Also have, open circuit voltage (Voc) is the voltage between two-terminal when being illustrated in the lead-out terminal of open solar cell single-cell module.Density of photocurrent (Jsc) is electric current (the every 1cm between the two-terminal of flowing in when being illustrated in the lead-out terminal that makes the solar cell single-cell module and being short-circuited
2).In addition, form factor (FF) is with the long-pending value (FF=Pmax/VocJsc) removing maximum output Pmax and obtain of open circuit voltage (Voc) with density of photocurrent (Jsc), and is the parameter of expression as the characteristic of the current-voltage characteristic curve of solar cell.Have again, photoelectric conversion efficiency (η) be that response current obtains by measuring with the voltage of power supply ammeter (source meter) scan light electric transition element, as the long-pending maximum output of voltage and electric current divided by every 1cm
2Luminous intensity and the value that obtains is multiplied by 100 and with the value that percentage is represented again, be by (maximum output/every 1cm
2Luminous intensity) * 100 represented.This result is shown in the table 1.
In addition, in order to estimate durability (long-term reliability), be determined at the photoelectric conversion efficiency of placing under the condition of 60 ℃ and 95%RH after 100 hours and in temperature cycling test (1 circulation 6 hours * 10 times) photoelectric conversion efficiency afterwards of having implemented 60 ℃～-20 ℃, and calculate the rate of change (%) respectively by (initial stage) photoelectric conversion efficiency of measuring earlier.Its result is shown in Table 1 by combined statement.
(embodiment 2)
Interpolation is the polyoxyethylene lauryl ether phosphoric acid of 30 weight % with respect to titania weight, and in addition, all the other all carry out with the method identical with embodiment 1, thereby modulates the titanium oxide colloid solution of embodiment 2.Then, except the titanium oxide colloid solution that uses this embodiment 2, all the other all carry out with the method identical with embodiment 1, thereby have produced the metal oxide electrode of embodiment 2, the electrode that supports pigment and dye-sensitized solar cell, and have carried out various mensuration.The result is shown in the table 1.
(embodiment 3)
At first, according to following steps modulation zinc oxide slurries.
Interpolation is the commercially available Zinc oxide particles (trade name: nanoZINC100 of 30 weight % with respect to toluene, Honjo Chemical system), further adding with respect to zinc oxide weight is the polyoxyethylene octadecyl ether phosphoric acid (trade name: Phosphanol RL-310, eastern nation chemical industry system) of 4 weight %.Afterwards, by carrying out 30 minutes dispersion treatment with paint mixer (paint shaker), thereby obtain the zinc oxide paste feed liquid of embodiment 3.
Then, use the zinc oxide paste feed liquid of the foregoing description 3 and make metal oxide electrode (zinc oxide electrode) with following steps.
At first, the ITO spatter film forming by will being approximately 600nm as the thickness of conducting film on the surface of polycarbonate film base material, thereby produce conductive polycarbonate film resin substrate (size: long 2.0cm, wide 1.5cm, thick 0.1mm with flexibility; Film resistor: 30 Ω/).Then, with the thickness that is provided with the square hole of long 0.5cm, wide 0.5cm is that the masking belt of 70 μ m is affixed on the conducting film of the conductive polycarbonate film resin substrate that is obtained, with the rotating speed of 500rpm with zinc oxide paste feed liquid rotary coating on the conducting film that is exposed in this square hole inboard.Afterwards, peel off masking belt, and with electric furnace 100 ℃ of following heat treated 30 minutes.Programming rate is 2 ℃/min.Carry out 5 above-mentioned rotary coating and heat treated repeatedly, thereby form the metal oxide layer (Zinc oxide film) that contains metal oxide and phosphoric acid based surfactant.
By above operation, thereby obtain on the conductive surface of matrix, to have the metal oxide electrode (zinc oxide electrode) of embodiment 3 of the metal oxide layer (Zinc oxide film) of containing metal oxide and phosphoric acid based surfactant.Measure the thickness of this metal oxide layer, be about 5 μ m.
Also have, make and above-mentioned same metal oxide electrode (zinc oxide electrode), it is carried out thermogravimetric analysis (TG), confirm that in its metal oxide layer (Zinc oxide film) polyoxyethylene octadecyl ether phosphoric acid is 3.5 weight % with respect to the content of zinc oxide.
In addition, make and above-mentioned same metal oxide electrode (zinc oxide electrode), estimate the dhering strength of its metal oxide layer (Zinc oxide film) on conductive polycarbonate film resin substrate.The evaluation of dhering strength is undertaken by gridiron pattern test (cross-cut test), tessellated grid is put into metal oxide layer (Zinc oxide film), and measure ratio (%) at the grid that remains in the metal oxide layer (Zinc oxide film) on the substrate behind the belt stripping test.Its results verification the ratio of grid of the Zinc oxide film that after disbonded test, left behind be 95%, have sufficient mechanical.
Afterwards, use the metal oxide electrode of the foregoing description 3, and make the electrode that supports pigment with following step.
Use D149 (Mitsubishi's system is made of paper) as sensitizing coloring matter, metal oxide electrode be impregnated in the D149 solution (tert-butyl alcohol/acetonitrile=1/1 mixed solvent) of 0.5mM and placed 1 hour.After the placement, take out electrode and cleaned air dry with acetonitrile.The metal oxide layer of having confirmed the electrode that obtained is owing to D149 support (absorption) becomes peony.
By above operation, support sensitizing coloring matter and the electrode that supports pigment of the embodiment 3 of the metal oxide layer that obtains thereby obtain on the conductive surface of matrix, to have at metal oxide surface.
Then, except the electrode that supports pigment that uses the foregoing description 3, all the other are all carried out with the method identical with embodiment 1, thereby produce the dye-sensitized solar cell of embodiment 3, and carry out various mensuration.The result is shown in the table 1.
(embodiment 4)
Interpolation is the polyoxyethylene octadecyl ether phosphoric acid of 1 weight % with respect to zinc oxide weight, and in addition, all the other all carry out with the method identical with embodiment 3, thereby modulates the zinc oxide paste feed liquid of embodiment 4.Then, except the zinc oxide paste feed liquid of using this embodiment 4, all the other are all carried out with the method identical with embodiment 3, thereby have produced the metal oxide electrode of embodiment 4, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(embodiment 5)
Interpolation is the polyoxyethylene octadecyl ether phosphoric acid of 10 weight % with respect to zinc oxide weight, and in addition, all the other all carry out with the method identical with embodiment 3, thereby modulates the zinc oxide paste feed liquid of embodiment 5.And, except the zinc oxide paste feed liquid of using this embodiment 5, all the other are all carried out with the method identical with embodiment 3, thereby have produced the metal oxide electrode of embodiment 5, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(embodiment 6)
Interpolation is the polyoxyethylene octadecyl ether phosphoric acid of 20 weight % with respect to zinc oxide weight, and in addition, all the other all carry out with the method identical with embodiment 3, thereby modulates the zinc oxide paste feed liquid of embodiment 6.And, except the zinc oxide paste feed liquid of using this embodiment 6, all the other are all carried out with the method identical with embodiment 3, thereby have produced the metal oxide electrode of embodiment 6, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(embodiment 7)
Interpolation is the polyoxyethylene octadecyl ether phosphoric acid of 30 weight % with respect to zinc oxide weight, and in addition, all the other all carry out with the method identical with embodiment 3, thereby modulates the zinc oxide paste feed liquid of embodiment 7.And, except the zinc oxide paste feed liquid of using this embodiment 7, all the other are all carried out with the method identical with embodiment 3, thereby have produced the metal oxide electrode of embodiment 7, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(embodiment 8)
Replace polyoxyethylene lauryl ether phosphoric acid and use polyoxyethylene dodecylphenyl ether phosphoric acid, in addition, all the other all carry out with the method identical with embodiment 1, thereby modulate the titanium oxide colloid solution of embodiment 8.And, except the titanium oxide colloid solution that uses this embodiment 8, all the other are all carried out with the method identical with embodiment 1, thereby have produced the metal oxide electrode of embodiment 8, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(embodiment 9)
Replace polyoxyethylene octadecyl ether phosphoric acid and use polyoxyethylene octadecyl phenyl ether phosphoric acid, in addition, all the other all carry out with the method identical with embodiment 3, thereby modulate the zinc oxide paste feed liquid of embodiment 9.And, except the zinc oxide paste feed liquid of using this embodiment 9, all the other are all carried out with the method identical with embodiment 3, thereby have produced the metal oxide electrode of embodiment 9, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(comparative example 1)
Except not adding polyoxyethylene lauryl ether phosphoric acid, all the other all carry out with the method identical with embodiment 1, thereby modulate the titanium oxide colloid solution of comparative example 1.And, except the titanium oxide colloid solution that uses this comparative example 1, all the other are all carried out with the method identical with embodiment 1, thereby have produced the metal oxide electrode of comparative example 1, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(comparative example 2)
Except not adding polyoxyethylene octadecyl ether phosphoric acid, all the other all carry out with the method identical with embodiment 3, thereby modulate the zinc oxide paste feed liquid of comparative example 2.And, except the zinc oxide paste feed liquid of using this comparative example 2, all the other are all carried out with the method identical with embodiment 3, thereby have produced the metal oxide electrode of comparative example 2, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(comparative example 3)
Use outside the polyethylene glycol (the pure medicine system of molecular weight 4000 and light) except replacing polyoxyethylene lauryl ether phosphoric acid, all the other all carry out with the method identical with embodiment 1, thereby modulate the titanium oxide colloid solution of comparative example 3.And, except the titanium oxide colloid solution that uses this comparative example 3, all the other are all carried out with the method identical with embodiment 1, thereby have produced the metal oxide electrode of comparative example 3, the electrode that supports pigment and dye-sensitized solar cell, carry out various mensuration.The result is shown in the table 1.
(comparative example 4)
Use except replacing polyoxyethylene lauryl ether phosphoric acid outside the sodium laureth sulfate (trade name: Emal 20C, flower king system), all the other all carry out with the method identical with embodiment 1, thereby modulate the titanium oxide colloid solution of comparative example 4.And, except the titanium oxide colloid solution that uses this comparative example 4, all the other are all carried out with the method identical with embodiment 1, thereby have produced the metal oxide electrode of comparative example 4, the electrode that supports pigment and dye-sensitized solar cell, and carry out various mensuration.The result is shown in the table 1.
Represented as embodiment 1～9 and comparative example 1 and 2, confirmed: contain phosphoric acid based surfactant in the metal oxide layer by making, mechanical strength that can tremendous raising metal oxide layer, and significantly improved the durability (long-term reliability) of dye-sensitized solar cell.In addition, also confirmed, can have both the battery behavior and the remarkable durability (long-term reliability) of the brilliance that prior art can not obtain by adjusting the content of phosphoric acid based surfactant.
In addition, according to the contrast of comparative example 3 and 4, confirmed: under the situation of the organic binder bond composition that uses prior art or other surfactant, the raising effect of durability (long-term reliability) that is not only the raising effect of mechanical strength of metal oxide layer and dye-sensitized solar cell is abundant inadequately, and even good battery behavior originally can not be brought into play.
Confirm thus: phosphoric acid based surfactant and other polymer compound or other surfactant are inequality, and it is a kind ofly can excessively not damage battery performance and can improve the special additive of the durability (long-term reliability) of the mechanical strength (film-strength, dhering strength) of metal oxide layer and dye-sensitized solar cell.
Also have, as previously discussed, the present invention is not limited to above-mentioned execution mode and embodiment, can do suitably change in the scope that does not break away from aim of the present invention.
Utilizability on the industry
As previously discussed, it is excellent and can excessively not damage battery behavior and can improve the electrode of durability to be implemented in the mechanical strength aspect of metal oxide layer, and, excellence aspect productivity ratio, economy and versatility, so the present invention can be extensively and is effectively utilized in electric material, electric device and possess in these the various machines, equipment, system etc., particularly can be effectively utilized in the field of photo-electric conversion element and coloring matter sensitization type solar cell.
Claims (7)
1. dye-sensitized solar cell metal oxide electrode is characterized in that:
Have matrix and the metal oxide layer that is arranged on this matrix,
Described metal oxide layer contains metal oxide and phosphoric acid based surfactant.
2. dye-sensitized solar cell metal oxide electrode as claimed in claim 1 is characterized in that:
Described metal oxide layer has the loose structure that the metal oxide particle cohesion forms.
3. dye-sensitized solar cell metal oxide electrode as claimed in claim 1 or 2 is characterized in that:
With respect to described metal oxide, contain the described phosphoric acid based surfactant of 0.1～30 weight %.
4. dye-sensitized solar cell is characterized in that:
Comprise:
Have matrix and the metal oxide electrode that is arranged at the metal oxide layer on this matrix;
With described metal oxide electrode be relative to the configuration to electrode; With
Be arranged at described metal oxide electrode and described to the electrolyte between the electrode;
Described metal oxide layer contains metal oxide and phosphoric acid based surfactant, and, supported sensitizing coloring matter.
5. dye-sensitized solar cell as claimed in claim 4 is characterized in that:
Described metal oxide layer has the loose structure that the metal oxide particle cohesion forms.
6. as claim 4 or 5 described dye-sensitized solar cells, it is characterized in that:
With respect to described metal oxide, contain the described phosphoric acid based surfactant of 0.1～30 weight %.
7. the manufacture method of a metal oxide electrode, this metal oxide electrode have matrix and are arranged at metal oxide layer on this matrix, it is characterized in that:
Described manufacture method comprises:
Preparation contains the operation of the concoction of metal oxide particle and phosphoric acid based surfactant;
Described concoction is placed operation on the matrix.
Applications Claiming Priority (2)
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| JP2009127545A JP5046195B2 (en) | 2009-05-27 | 2009-05-27 | Metal oxide electrode for dye-sensitized solar cell, dye-sensitized solar cell, and method for producing metal oxide electrode |
| JP2009-127545 | 2009-05-27 |
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| US (1) | US20100300515A1 (en) |
| EP (1) | EP2256763A3 (en) |
| JP (1) | JP5046195B2 (en) |
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| KR101048044B1 (en) * | 2009-07-02 | 2011-07-13 | 건국대학교 산학협력단 | Dye-sensitized solar cell production equipment and production method through roll-to-roll continuous process |
| KR101156545B1 (en) * | 2010-12-24 | 2012-06-20 | 삼성에스디아이 주식회사 | Photoelectrode of dye sensitized solar cell, method of the same and solar cell using the same |
| JP2012204169A (en) * | 2011-03-25 | 2012-10-22 | Sony Corp | Dye sensitized photoelectric conversion element and method for manufacturing the same, and method for forming metal oxide semiconductor layer |
| WO2014042449A2 (en) * | 2012-09-12 | 2014-03-20 | 한국화학연구원 | Solar cell having light-absorbing structure |
| WO2015085441A1 (en) * | 2013-12-12 | 2015-06-18 | Nanograde Ag | Electronic devices comprising solution-processable metal oxide buffer layers |
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| JP2006012490A (en) * | 2004-06-23 | 2006-01-12 | Hitachi Chem Co Ltd | Mixed aqueous solution for semiconductor electrode, semiconductor electrode, photoelectric conversion element, solar cell, and manufacturing method for them |
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| EP2028667A2 (en) * | 2007-08-21 | 2009-02-25 | Electronics And Telecommunications Research Institute | Dye-sensitized solar cell and method of manufacturing the same |
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| JP5081345B2 (en) | 2000-06-13 | 2012-11-28 | 富士フイルム株式会社 | Method for manufacturing photoelectric conversion element |
| CN1269257C (en) * | 2001-02-21 | 2006-08-09 | 昭和电工株式会社 | Metal oxide dispersion and photoactive electrode for dye-sensitized solar cell, and dye-sensitized solar cell |
| JP2004119129A (en) | 2002-09-25 | 2004-04-15 | Tokai Rubber Ind Ltd | Manufacturing method of dye-sensitized solar cell, and dye-sensitized solar cell obtained by it |
| US20090014062A1 (en) * | 2004-01-22 | 2009-01-15 | Showa Denko K.K. | Metal Oxide Dispersion, Metal Oxide Electrode Film, and Dye Sensitized Solar Cell |
| JP4595337B2 (en) | 2004-02-06 | 2010-12-08 | 東洋製罐株式会社 | Method for producing negative electrode in dye-sensitized solar cell |
| JP2005251591A (en) | 2004-03-04 | 2005-09-15 | Toyo Seikan Kaisha Ltd | Manufacturing method of negative electrode in dye-sensitized solar cell |
| JP4982067B2 (en) | 2005-10-07 | 2012-07-25 | グンゼ株式会社 | Method for producing photoelectrode for dye-sensitized solar cell |
| JP2007261121A (en) * | 2006-03-29 | 2007-10-11 | Ricoh Co Ltd | Method for cleaning reversible thermal recording medium |
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|---|---|---|---|---|
| JP2006012490A (en) * | 2004-06-23 | 2006-01-12 | Hitachi Chem Co Ltd | Mixed aqueous solution for semiconductor electrode, semiconductor electrode, photoelectric conversion element, solar cell, and manufacturing method for them |
| CN101075660A (en) * | 2006-05-18 | 2007-11-21 | 三星电子株式会社 | Semiconductor electrode containing phosphate and solar cell using the same |
| JP2007311336A (en) * | 2006-05-18 | 2007-11-29 | Samsung Electronics Co Ltd | Semiconductor electrode containing phosphate and solar battery using the same |
| EP2028667A2 (en) * | 2007-08-21 | 2009-02-25 | Electronics And Telecommunications Research Institute | Dye-sensitized solar cell and method of manufacturing the same |
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| JP5046195B2 (en) | 2012-10-10 |
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| US20100300515A1 (en) | 2010-12-02 |
| JP2010277762A (en) | 2010-12-09 |
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